US4338239A - Polyacrylate thickening agents - Google Patents
Polyacrylate thickening agents Download PDFInfo
- Publication number
- US4338239A US4338239A US06/248,164 US24816481A US4338239A US 4338239 A US4338239 A US 4338239A US 24816481 A US24816481 A US 24816481A US 4338239 A US4338239 A US 4338239A
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- interpolymer
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- ether
- acid
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Classifications
-
- C—CHEMISTRY; METALLURGY
- C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
- C09D—COATING COMPOSITIONS, e.g. PAINTS, VARNISHES OR LACQUERS; FILLING PASTES; CHEMICAL PAINT OR INK REMOVERS; INKS; CORRECTING FLUIDS; WOODSTAINS; PASTES OR SOLIDS FOR COLOURING OR PRINTING; USE OF MATERIALS THEREFOR
- C09D11/00—Inks
- C09D11/02—Printing inks
- C09D11/03—Printing inks characterised by features other than the chemical nature of the binder
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
- C08F220/00—Copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and only one being terminated by only one carboxyl radical or a salt, anhydride ester, amide, imide or nitrile thereof
- C08F220/02—Monocarboxylic acids having less than ten carbon atoms; Derivatives thereof
- C08F220/04—Acids; Metal salts or ammonium salts thereof
-
- C—CHEMISTRY; METALLURGY
- C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
- C09D—COATING COMPOSITIONS, e.g. PAINTS, VARNISHES OR LACQUERS; FILLING PASTES; CHEMICAL PAINT OR INK REMOVERS; INKS; CORRECTING FLUIDS; WOODSTAINS; PASTES OR SOLIDS FOR COLOURING OR PRINTING; USE OF MATERIALS THEREFOR
- C09D7/00—Features of coating compositions, not provided for in group C09D5/00; Processes for incorporating ingredients in coating compositions
- C09D7/40—Additives
- C09D7/43—Thickening agents
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
- C08L33/00—Compositions of homopolymers or copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and only one being terminated by only one carboxyl radical, or of salts, anhydrides, esters, amides, imides or nitriles thereof; Compositions of derivatives of such polymers
- C08L33/02—Homopolymers or copolymers of acids; Metal or ammonium salts thereof
-
- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y10—TECHNICAL SUBJECTS COVERED BY FORMER USPC
- Y10S—TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y10S526/00—Synthetic resins or natural rubbers -- part of the class 520 series
- Y10S526/932—Thickener or dispersant for aqueous system
Definitions
- thickening agents are natural gums and resins such as starch, gum arabic, modified starch products, dextrins, sodium alginates, tragacanths, and the like.
- Synthetic materials employed as thickening agents include carboxymethylcellulose, polyvinyl alcohol, polyacrylamide, polyacrylic acids and salts thereof, methylcellulose, carboxymethylcellulose, hydroxyethylcellulose, polyvinylpyrrolidone, polyvinylmethylether, polyethyleneoxides, and copolymers of polyvinylmethylether and maleic anhydride.
- Thickeners of the polyelectrolyte type include synthetic polymeric water-soluble polymers such as the sodium polyacrylates as well as the copolymers of various acrylates, such as are described in U.S. Pat. Nos. 2,798,053; 2,883,351; 2,956,046; 3,035,004; 3,436,378; 3,915,921 and 4,167,502.
- Water-soluble polyelectrolyte copolymers employed as thickeners include those esters prepared by the esterification reaction between the acid anhydride groups of a copolymer of an alkylvinylether and maleic anhydride with the terminal hydroxyl groups of a nonionic surfactant of an alkylphenoxyethoxyethanol polymer.
- the resulting water-soluble polymer is a partial ester which contains free acid groups suitable for subsequent neutralization with a basic material, such as an amine or a metal oxide or hydroxide.
- thickening agents are carboxylic acid polymers made by copolymerizing acrylic acid with a small amount of a polyallyl polyether of a polyhydric alcohol, e.g., polyallyl sucrose. Such polymers are insoluble in water. The alkali metal salts of which swell in water to form gel like compositions.
- Print pastes always contain a thickening agent (besides dyes, binders and other auxiliaries) which provides them with the required degree of viscosity.
- the thickening agent should be compatible with the conventional components of a textile print paste and should not impair either the dye yield or the fastness of the print. In the case of prints which have been prepared with print pastes containing conventional thickeners, they are often sensitive to squeezing so that a lower dye yield is obtained.
- polyacrylic acid thickening agents of the prior art have generally been associated with the production of harsh hands when they have been used for thickening of impregnating materials for textiles, such as pigment-printing and dyeing compositions. They are also characterized by difficulty in formulation and impairment of water-resistance of the textile or other article treated with compositions containing the known thickeners of this type.
- thickening agents which contain 10-40 percent acrylic acid or methacrylic acid do not permit the coloristic effect of pigmentary printing pastes to be sufficiently emphasized.
- the least concentration of thickening agent is employed. In this case, a poor retention of the aqueous phase occurs, which leads to spreading or running effects, and results in prints with diffused outlines.
- One or more objects of the present invention are accomplished by the provision of an interpolymer of monomers comprising (1) at least 60 weight percent of acrylic acid or methacrylic acid; (2) between about 0.2-20 weight percent of a glyceryl ether derivative in which one hydroxy group is in the free form, one hydroxyl group in in the form of an allyl ether substituent, and the other hydroxyl group is in the form of an ether or ester substituent; and (3) between about 0-20 weight percent of another olefinically unsaturated monomer copolymerizable therewith.
- the interpolymer normally has a molecular weight in the range between about 10,000-1,000,000.
- a typical interpolymer will have a molecular weight in the range between about 20,000-200,000.
- the molecular weight can be determined by any method well known in the art and can be expressed as number average or as weight average molecular weight.
- the (meth) acrylic acid component can be at least partially replaced by other acrylic acid type monomers such as ethacrylic acid, ⁇ -chloroacrylic acid, ⁇ -phenylacrylic acid, ⁇ -cyanoacrylic acid, itaconic acid, crotonic acid and the like.
- this monomer is prepared by reacting allyl glycidyl ether with a monohydric alcohol or a monocarboxylic acid in the mole ratio of allyl glycidyl ether to alcohol or acid of about 1:1 to about 1:0.5.
- the monohydric alcohols are: alkyl alcohols which contain from one to 20 carbon atoms; arylalkyl alcohols which contain from 7 to 20 carbon atoms; alkenyl alcohols which contain from 12 to 20 carbon atoms; and glycol and polyglycol monoethers having the formula:
- R is an alkyl group which contains from 1 to 10 carbon atoms or an aryl group which is phenyl or alkyl substituted phenyl group wherein the alkyl group contains from 1 to 12 carbon atoms and wherein n has a value of 1 to about 40.
- the monocarboxylic acids are alkyl monocarboxylic acids which contain from 2 to 20 carbon atoms; arylmonocarboxylic acids which contain 7 to 20 carbon atoms; or alkenyl monocarboxylic acids which contain from 5 to 20 carbon atoms.
- the glyceryl ether derivative monomer component of the interpolymer before polymerization can be represented by the formula: ##STR1## wherein Y is an ether or ester group which results from the reaction of allyl glycidyl ether with the alcohols or acids described hereinbefore.
- the glyceryl ether derivative monomer has a molecular weight which ranges up to about 2000 as calculated from the molecular weights of the reactants.
- the glyceryl ether monomer is prepared by the reaction of allyl glycidyl ether with an appropriate alcohol at a moderate temperature (e.g., 70° C.) in the presence of a Lewis acid catalyst (e.g., boron trifluoride etherate): ##STR2##
- a Lewis acid catalyst e.g., boron trifluoride etherate
- allyl glycidyl ether and the appropriate monohydric alcohol are reacted in the mole ratio of allyl glycidyl ether to alcohol of 1:1 to 1:0.5 and, preferably, 1:0.95 to 1:0.8.
- alkanols and arylalkanols which contain from 1 to about 20 carbon atoms, such as methanol, isopropanol, butanol, 2-ethylhexanol, cetyl alcohol, lauryl alcohol, stearyl alcohol, cyclohexanol, benzyl alcohol, and the like.
- Additional alcohols are the alcohols which contain ethylenic unsaturation, such as olelyl alcohol, linolelyl alcohol, palmitolelyl alcohol and the like, i.e., such unsaturated alcohols which contain 12 to about 20 carbon atoms per molecule.
- Other alcohols are the glycol and polyglycol monoethers, i.e., alcohols which can be represented as follows:
- R is an alkyl group which contains from 1 to about 10 carbon atoms or an aryl group with or without alkyl substitution, and wherein n has a value of 1 to about 40.
- examples of such alcohols are the monomethyl ether of ethylene glycol, the monobutyl ether of ethylene glycol, the mono-2-ethylhexyl ether of ethylene glycol, the monomethyl ether of diethylene glycol, the monomethyl ether of polyethylene glycol having a molecular weight of about 350, the monophenyl ether of polyethylene glycol having a molecular weight of about 800, the nonylphenyl ether of polyethylene glycol having a molecular weight of about 1100, and the like.
- Additional alcohols are those based on propylene oxide rather than ethylene oxide and on block copolymers of ethylene oxide and propylene oxide.
- the glyceryl ether monomer derivative contains an ester group
- it is prepared by reacting allyl glycidyl ether with an appropriate monocarboxylic acid at a moderate temperature (e.g., 70° C.) up to the boiling point of allyl glycidyl ether (154° C.) but preferably at about 80° to about 100° C. in the presence of a basic catalyst, a tertiary amine, tertiary amine salt, quaternary ammonium salt or a metal complex catalyst: ##STR3##
- allyl glycidyl ether and the appropriate monocarboxylic acid are reacted in the mole ratio of allyl glycidyl ether to acid of 1:1 to about 1:0.8 and preferably 1:0.95 to 1:0.85.
- Useful monocarboxylic acids are alkyl or aryl monocarboxylic acids which contain 2 to 20 carbon atoms or alkenyl monocarboxylic acids which contain 5 to 20 carbon atoms.
- Examples of such acids are acetic acid, butyric acid, hexanoic acid, pelargonic acid, capric acid, lauric acid, palmitic acid, arachidic acid, benzoic acid, naphthoic acid, oleic acid, linoleic acid, ricinoleic acid, undecylenic acid and the like.
- the interpolymer can contain up to about 20 weight percent of one or more other monomers which are copolymerizable with the said (meth)acrylic acid and glyceryl ether monomer components.
- Suitable monomers include acrylamide, methacrylamide, N-ethylacrylamide, N,N-dimethylacrylamide, styrene, acrylonitrile, methacrylonitrile, methyl acrylate, ethyl acrylate, propyl acrylate, butyl acrylate, hexyl acrylate, octyl acrylate, methyl methacrylate, vinyl acetate, vinyl propionate, vinyl butyrate, dimethyl maleate, diethyl maleate, dimethyl fumarate, diethyl fumarate, monomethyl maleate, monoethyl fumarate, maleic anhydride, and the like.
- the preferred method of preparing the above defined interpolymer is by the polymerization of the mixture of the constituent monomers in an inert organic diluent having some solublizing action on one or more of the monomeric ingredients but substantially none on the resultant interpolymer.
- Polymerization in an aqueous medium containing a water-soluble free-radical catalyst is an operative method but is less desirable than polymerization in the organic inert diluent.
- the product is recovered as a highly swollen gel, which may be used directly or further dried and subdivided.
- Suitable diluents include benzene, toluene, xylene, ethylbenzene, tetralin, hexane, heptane, octane, carbon tetrachloride, ethylene dichloride, bromotrichloromethane, chlorobenzene, acetone, methyl ethyl ketone, and the like.
- the polymerization in the diluent medium may be carried out in the presence of a free-radical catalyst in a closed vessel containing an inert atmosphere and under autogenous pressure or artificially-induced pressure, or in an open vessel under reflux at atmospheric pressure.
- the temperature of the polymerization may be varied from about 0° C. to 100° C. or higher, more preferably from 20° C. to 90° C., the temperature depending to a large degree upon the activity of the monomers and catalyst used and the molecular weight desired in the polymeric product.
- the molecular weights of the product interpolymers are greater for those made in the lower temperature range than for those made in the higher temperature range.
- Polymerization at 50° C. to 90° C. under atmospheric pressure employing a free-radical catalyst generally provides a polymer yield of 90 to about 100 percent of theory in less than 20 hours, usually in less than 5 hours.
- Suitable free-radical catalysts include peroxides such as sodium, potassium and ammonium persulfates, caprylyl peroxide, benzoyl peroxide, pelargonyl peroxide, hydrogen peroxide, cumene hydroperoxide, tertiary butyl diperphthalate, tertiary butyl perbenzoate, sodium peracetate, sodium percarbonate, azobisisobutyronitrile, and the like.
- Other useful catalysts are the so-called "redox" type of catalyst and the heavy-metal activated catalyst systems. Generally, between about 0.01-2.5 percent by weight or more of catalyst based on monomer weight is sufficient in the invention process.
- this invention provides a thickened liquid composition which contains an effective quantity of a thickening agent which as described above is an interpolymer of monomers comprising (1) at least 60 weight percent of acrylic acid or methacrylic acid; (2) between about 0.2-20 weight percent of a glyceryl ether derivative in which one hydroxyl group is in the free form, one hydroxyl group is in the form of an allyl ether substituent, and the other hydroxyl group is in the form of an ether or ester substituent; and (3) between about 0-20 weight percent of another olefinically unsaturated monomer copolymerizable therewith.
- a thickening agent which as described above is an interpolymer of monomers comprising (1) at least 60 weight percent of acrylic acid or methacrylic acid; (2) between about 0.2-20 weight percent of a glyceryl ether derivative in which one hydroxyl group is in the free form, one hydroxyl group is in the form of an allyl ether substituent, and the other hydroxyl group is in
- the quantity of thickening agent in the liquid composition will average in the range between about 0.1-5 weight percent, based on the weight of liquid medium.
- the liquid medium usually is a polar solvent which is capable of dissolving or partially dissolving or at least is capable of being thickened by the thickening agent.
- suitable solvents and miscible mixtures thereof are esters such as ethyl, butyl, amyl, ethoxyethyl and methoxyethyl acetates, lactates, and propionates; ketones such as acetone, methyl isopropyl ketone, methyl isobutyl ketone, dioxane, isophorone, and cyclohexanone; alcohols such as n-butanol, t-butanol, isopropyl alcohol, n-propyl alcohol, amyl alcohol, and cyclohexanol; ethers such as diethyl ether, monoethyl ether of ethylene glycol, monomethyl ether of ethylene glycol, and monobutyl ether of ethylene glycol; and miscellane
- the maximum viscosity is attained when the carboxylic acid groups in the interpolymer are at least partially neutralized to a neutral or alkaline pH.
- the neutralization preferably is accomplished with basic agents such as sodium, potassium and ammonium hydroxides, carbonates and bicarbonates.
- An aqueous medium containing between about 0.1-5 weight percent of interpolymer and having a pH between about 5-9, will generally exhibit a viscosity between about 20,000-60,000 cps at 25° C. (Brookfield, spindle No. 6, 20 rpm).
- the interpolymer can be neutralized with organic bases such as primary, secondary and tertiary amines.
- organic bases such as primary, secondary and tertiary amines.
- Typical amines include monoethanolamine, dimethylamine, triethylamine, triethanolamine, and the like.
- the above-described thickened liquid composition is uniquely adapted for the formulation of print pastes which exhibit high dye yield and print brilliance, low sensitivity to squeezing by printing machine rollers, and stability to coagulation of binder emulsions when pigments are added.
- the invention thickened liquid composition is compatible with dye components such as vat dyes, direct dyes, disperse dyes, reactive dyes and metal complex dyes.
- the thickened liquid composition can also be combined with pigment dyes in the presence of binders.
- binders are polymers of esters of acrylic or methacrylic acid and aliphatic alcohols with 1 to 4 carbon atoms with such comonomers as styrene, butadiene, vinylchloride, acrylonitrile, acrylamide, N-methylolacrylamide and 1,4-butanediol mono- and di-acrylate.
- Such polymers may be applied in combination with aminoplast precondensates, e.g., urea or its cyclic or acrylic derivatives, or melamine and formaldehyde.
- the present invention thickening agent in the print paste performs as an emulsifier so that pigment print pastes which contain a pigment binder can be used on textile printing machines;
- a print paste can be prepared in the manner described in U.S. Pat. No. 3,878,151 by blending together the thickening agent, water, dye, and optionally a mineral spirit.
- a film-forming aqueous copolymer dispersion is added to the print paste.
- a present invention interpolymer can be employed as a thickening or bodying agent, for example, in cosmetics, shampoos, toothpastes, ointments, detergents, polymer emulsions (e.g., latex paints), oil well drilling compositions, and the like.
- Allyl glycidyl ether (114 grams, 1 mole) is then added dropwise over a period of one hour at 70° C.
- the exothermic heat of reaction is controlled by intermittent cooling.
- the reaction is completed by maintaining the reaction medium at 70° C. for two hours.
- a one-liter three-neck flask equipped with stirrer, add funnel, thermometer and condenser is charged with 300 grams of toluene.
- the toluene is heated to 80° C. with stirring under a sweep of nitrogen.
- a solution of 95 grams of acrylic acid, 5 grams of allyl glycidyl ether-benzyl alcohol adduct (1:0.95 molar) and 0.05 gram of azobisisobutyronitrile (AIBN) is added to the flask over a period of two hours, while maintaining the exothermic reaction medium at 80° C.
- the mixture is held at 80° C. for two or more hours, and then 20 milligrams of AIBN (in acetone) are added. After an additional hour at 90° C., the reaction product mixture is cooled and filtered.
- the precipitated solid polymer is recovered, washed with toluene, and dried overnight in a forced air oven at 125° F.
- the yield of dry polymer is 96.6 grams.
- a 0.5 weight percent solution of the polymer in deionized water is produced by neutralizing the aqueous medium with 10 percent sodium hydroxide.
- the solution exhibits a Brookfield viscosity of 38,500 cps (Spindle No. 6, 20 rpm).
- glyceryl ether derivatives of allyl glycidylether and Igepal CO-710 ethoxylated nonyl phenol having an average molecular weight of 682 are prepared wherein the mole ratio of allyl glycidyl ether to Igepal CO-710 is varied from 1:1.04 to 1:0.5.
- Copolymers of 15 parts of the allyl derivative monomers and 85 parts of acrylic acid are made using the same procedure as described in Example I. Aqueous solutions of the copolymers are prepared and the viscosities are measured as described in Example I.
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Abstract
Description
RO(C.sub.2 H.sub.4 O).sub.n H
RO(C.sub.2 H.sub.4 O).sub.n H
______________________________________ AGE.sup.(1) Monomer Reactant Mole Ratio Monomers Mole Ratio ______________________________________ 90/5/5 AA.sup.(2) /N,N-dimethylacrylamide/ 1/0.95 AGE-butyl Carbitol.sup.(3) 93/7 AA/AGE-cetyl alcohol 1/0.9 85/15 AA/AGE-Igepal CO-800.sup.(4) 1/0.9 96/4 AA/AGE-oleyl alcohol 1/0.9 94/6 AA/AGE-butyl carbitol 1/0.95 98/2 AA/AGE-undecylenic acid 1/0.95 85/15 AA/AGE-Igepal CO-850.sup.(5) 1/0.9 94/6 AA/AGE-methoxy Carbowax 350.sup.(6) 1/0.9 95/5 AA/AGE-isodecyl alcohol 1/0.9 ______________________________________ Highly viscous solution of these polymers are formed in water using the procedure described in Example I. .sup.(1) Allyl glycidyl ether. .sup.(2) Acrylic acid. .sup.(3) Monobutyl ether of diethylene glycol (Union Carbide). .sup.(4) Ethoxylated nonylphenol; Avg. M.W. 1540 (G.A.F.). .sup.(5) Ethoxylated nonylphenol: Avg. M.W. 1100 (G.A.F.). .sup.(6) Monomethyl ether of polyethyleneglycol; M.W. 350 (Union Carbide)
______________________________________ Mole Ratio of Brookfield Viscosity (20 RPM, RVT) Allyl Glycidyl Ether 0.5% Neutralized Aqueous Igepal CO-710 Solution of Copolymer ______________________________________ 1:1.04 1,040 cps 1:1 22,875 cps 1:0.96 27,850 cps 1:0.9 26,500 cps 1:0.5 6,400 cps (1% solution) ______________________________________
Claims (17)
RO(C.sub.2 H.sub.4 O).sub.n H
RO(C.sub.2 H.sub.4 O).sub.n H
Priority Applications (3)
Application Number | Priority Date | Filing Date | Title |
---|---|---|---|
US06/248,164 US4338239A (en) | 1980-10-10 | 1981-03-30 | Polyacrylate thickening agents |
EP81304596A EP0050923A3 (en) | 1980-10-10 | 1981-10-05 | Polyacrylate thickening agents |
CA000387590A CA1203347A (en) | 1980-10-10 | 1981-10-08 | Polyacrylate thickening agents |
Applications Claiming Priority (2)
Application Number | Priority Date | Filing Date | Title |
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US19600980A | 1980-10-10 | 1980-10-10 | |
US06/248,164 US4338239A (en) | 1980-10-10 | 1981-03-30 | Polyacrylate thickening agents |
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US19600980A Continuation-In-Part | 1980-10-10 | 1980-10-10 |
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US4338239A true US4338239A (en) | 1982-07-06 |
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US06/248,164 Expired - Lifetime US4338239A (en) | 1980-10-10 | 1981-03-30 | Polyacrylate thickening agents |
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US (1) | US4338239A (en) |
EP (1) | EP0050923A3 (en) |
CA (1) | CA1203347A (en) |
Cited By (34)
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US4529773A (en) * | 1982-03-17 | 1985-07-16 | David Witiak | Alkali-soluble emulsion polymers in acidic surfactant compositions |
US4745154A (en) * | 1986-04-14 | 1988-05-17 | Alco Chemical Corporation | Water soluble polymers, their preparation and their uses |
US4814514A (en) * | 1986-05-07 | 1989-03-21 | Dai-Ichi Kogyo Seiyaku Co., Ltd. | Surface active compounds having a polymerizable moiety |
US4847410A (en) * | 1987-07-30 | 1989-07-11 | Olin Corporation | Block co-polymers useful as aqueous dispersants |
US4892916A (en) * | 1984-08-15 | 1990-01-09 | Allied Colloids Limited | Polymeric thickeners and their production |
US4959156A (en) * | 1987-07-30 | 1990-09-25 | Olin Corporation | Block co-polymers useful as aqueous dispersants |
US4978460A (en) * | 1985-05-03 | 1990-12-18 | Bluecher Hubert | Aqueous swollen macromolecule-containing system as water for firefighting |
US5086142A (en) * | 1989-07-29 | 1992-02-04 | Th. Goldschmidt Ag | Copolymer acting as thickening agent for aqueous preparations having a ph above 5.5, a method for its preparation and its use as a thickening agent |
US5190110A (en) * | 1985-05-03 | 1993-03-02 | Bluecher Hubert | Use of an aqueous swollen macromolecule-containing system as water for fire fighting |
US5292843A (en) * | 1992-05-29 | 1994-03-08 | Union Carbide Chemicals & Plastics Technology Corporation | Polymers containing macromonomers |
US5292828A (en) * | 1992-05-29 | 1994-03-08 | Union Carbide Chemicals & Plastics Technology Corporation | Polymers containing complex hydrophobic groups |
DE4242039A1 (en) * | 1992-12-12 | 1994-06-16 | Stockhausen Chem Fab Gmbh | Copolymers and their use for the treatment of leather |
US5399618A (en) * | 1993-06-28 | 1995-03-21 | Union Carbide Chemical & Plastics Technology Corporation | Processes for preparing aqueous polymer emulsions |
US5403821A (en) * | 1988-11-09 | 1995-04-04 | Nippon Shokubai Kagaku Kogyo Co., Ltd. | Drilling fluid additives |
US5426182A (en) * | 1992-05-29 | 1995-06-20 | Union Carbide Chemical & Plastics Technology Corporation | Polysaccharides containing complex hydrophobic groups |
US5461100A (en) * | 1992-05-29 | 1995-10-24 | Union Carbide Chemicals & Plastics Technology Corporation | Aircraft anti-icing fluids |
US5476885A (en) * | 1989-07-25 | 1995-12-19 | Nippon Shokubai Co., Ltd. | Cement additive, method for producing the same, and cement composition |
US5478602A (en) * | 1992-05-29 | 1995-12-26 | Union Carbide Chemicals & Plastics Technology Corporation | Polymers containing macromonomers and their use in a method of coating substrates |
US5486587A (en) * | 1992-05-29 | 1996-01-23 | Union Carbide Chemicals & Plastics Technology Corporation | Aqueous latexes containing macromonomers |
US5488180A (en) * | 1992-05-29 | 1996-01-30 | Union Carbide Chemicals & Plastics Technology Corporation | Complex hydrophobe compounds |
US5663123A (en) * | 1992-07-15 | 1997-09-02 | Kb Technologies Ltd. | Polymeric earth support fluid compositions and method for their use |
US5703174A (en) * | 1995-06-21 | 1997-12-30 | W. R. Grace & Co.-Conn. | Air controlling superplasticizers |
US5714543A (en) * | 1994-01-13 | 1998-02-03 | Bristol-Myers Squibb Company | Water soluble polymer additives for polyurethane-based pressure sensitive adhesives |
US5739378A (en) * | 1992-05-29 | 1998-04-14 | Union Carbide Chemicals & Plastics Technology Corporation | Complex hydrophobe-containing oligomers |
US5863973A (en) * | 1995-01-16 | 1999-01-26 | Union Carbide Chemicals & Plastics Technology Corporation | Process of making aircraft deicing/anti-icing fluids thickened by associative polymers |
US6139623A (en) * | 1997-01-21 | 2000-10-31 | W. R. Grace & Co.-Conn. | Emulsified comb polymer and defoaming agent composition and method of making same |
US6248697B1 (en) | 1997-02-12 | 2001-06-19 | Kb Technologies, Ltd. | Composition and method for a dual-function soil-grouting excavating or boring fluid |
US20020123433A1 (en) * | 1997-02-12 | 2002-09-05 | Goodhue K. Gifford | Composition and method for dual function soil grouting excavating or boring fluid |
US6451880B1 (en) | 1998-11-23 | 2002-09-17 | W. R. Grace & Co.-Conn. | Workability and board life in masonry mortar and method for obtaining same |
US20040072979A1 (en) * | 2002-10-15 | 2004-04-15 | Ashland, Inc. | Oligomers from multifunctional acrylates |
US20060155022A1 (en) * | 2002-09-02 | 2006-07-13 | Anne Hupp | Aqueous pigment pastes containing metallic pigments and the use thereof for producing substances for decorative aqueous coatings |
US20080221293A1 (en) * | 2005-09-29 | 2008-09-11 | Nippon Shokubia Co., Ltd | Polyalkylene Glycol Monomer, Polyalkylene Glycol Polymer Containing the Same, and Application Thereof |
US7465774B1 (en) * | 1992-04-23 | 2008-12-16 | Basf Aktiengesellscahft | Use of copolymers of carboxylic acids and long-chain compounds with isolated C-C multiple bonds as thickeners or dispersants |
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---|---|---|---|---|
US4657590A (en) * | 1984-10-22 | 1987-04-14 | The First National Bank Of Cincinnati | Basic dye ink formulations and methods |
US6889061B2 (en) | 2000-01-27 | 2005-05-03 | Celletra Ltd. | System and method for providing polarization matching on a cellular communication forward link |
Citations (14)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
US2798053A (en) * | 1952-09-03 | 1957-07-02 | Goodrich Co B F | Carboxylic polymers |
US2883351A (en) * | 1954-09-02 | 1959-04-21 | Phillips Petroleum Co | Process for creaming rubber latices and creaming agent used |
US2956046A (en) * | 1954-09-21 | 1960-10-11 | Rohm & Haas | Polymerization of acrylic acid salts and the like |
US3035004A (en) * | 1955-03-25 | 1962-05-15 | Rohm & Haas | Aqueous polymer dispersions containing (c1-c8)-alkyl acrylate/methacrylic acid copolymer salt thickeners |
US3426004A (en) * | 1965-01-13 | 1969-02-04 | Goodrich Co B F | Crosslinked acrylic acid interpolymers |
US3436378A (en) * | 1966-06-14 | 1969-04-01 | Gaf Corp | Novel interpolymers useful as thickening agents |
US3817949A (en) * | 1971-03-30 | 1974-06-18 | Manuf De Prod Chimiques Protex | Unsaturated acid-allyl acetal polymers |
US3878151A (en) * | 1968-05-28 | 1975-04-15 | Basf Ag | Thickeners for print pastes composed of cross-linked maleic anhydride-alkyl vinyl ether polymers |
US3894980A (en) * | 1973-04-30 | 1975-07-15 | Rohm & Haas | Thickener |
US3907730A (en) * | 1973-09-27 | 1975-09-23 | Goodrich Co B F | Resinous initiator suspension for olefinic polymerization reactions |
US3915921A (en) * | 1974-07-02 | 1975-10-28 | Goodrich Co B F | Unsaturated carboxylic acid-long chain alkyl ester copolymers and tri-polymers water thickening agents and emulsifiers |
US3978016A (en) * | 1973-04-27 | 1976-08-31 | Produits Chimiques Ugine Kuhlmann | Pigmentary printing pastes for textiles |
US4138381A (en) * | 1975-04-14 | 1979-02-06 | E. I. Du Pont De Nemours And Company | Polymeric thickeners, processes for their preparation and uses thereof |
US4167502A (en) * | 1972-12-06 | 1979-09-11 | Rohm And Haas Company | Carboxylic polymeric thickeners |
Family Cites Families (1)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
US3268492A (en) * | 1962-06-12 | 1966-08-23 | Celanese Corp | Terpolymer |
-
1981
- 1981-03-30 US US06/248,164 patent/US4338239A/en not_active Expired - Lifetime
- 1981-10-05 EP EP81304596A patent/EP0050923A3/en not_active Withdrawn
- 1981-10-08 CA CA000387590A patent/CA1203347A/en not_active Expired
Patent Citations (14)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
US2798053A (en) * | 1952-09-03 | 1957-07-02 | Goodrich Co B F | Carboxylic polymers |
US2883351A (en) * | 1954-09-02 | 1959-04-21 | Phillips Petroleum Co | Process for creaming rubber latices and creaming agent used |
US2956046A (en) * | 1954-09-21 | 1960-10-11 | Rohm & Haas | Polymerization of acrylic acid salts and the like |
US3035004A (en) * | 1955-03-25 | 1962-05-15 | Rohm & Haas | Aqueous polymer dispersions containing (c1-c8)-alkyl acrylate/methacrylic acid copolymer salt thickeners |
US3426004A (en) * | 1965-01-13 | 1969-02-04 | Goodrich Co B F | Crosslinked acrylic acid interpolymers |
US3436378A (en) * | 1966-06-14 | 1969-04-01 | Gaf Corp | Novel interpolymers useful as thickening agents |
US3878151A (en) * | 1968-05-28 | 1975-04-15 | Basf Ag | Thickeners for print pastes composed of cross-linked maleic anhydride-alkyl vinyl ether polymers |
US3817949A (en) * | 1971-03-30 | 1974-06-18 | Manuf De Prod Chimiques Protex | Unsaturated acid-allyl acetal polymers |
US4167502A (en) * | 1972-12-06 | 1979-09-11 | Rohm And Haas Company | Carboxylic polymeric thickeners |
US3978016A (en) * | 1973-04-27 | 1976-08-31 | Produits Chimiques Ugine Kuhlmann | Pigmentary printing pastes for textiles |
US3894980A (en) * | 1973-04-30 | 1975-07-15 | Rohm & Haas | Thickener |
US3907730A (en) * | 1973-09-27 | 1975-09-23 | Goodrich Co B F | Resinous initiator suspension for olefinic polymerization reactions |
US3915921A (en) * | 1974-07-02 | 1975-10-28 | Goodrich Co B F | Unsaturated carboxylic acid-long chain alkyl ester copolymers and tri-polymers water thickening agents and emulsifiers |
US4138381A (en) * | 1975-04-14 | 1979-02-06 | E. I. Du Pont De Nemours And Company | Polymeric thickeners, processes for their preparation and uses thereof |
Cited By (53)
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US4529773A (en) * | 1982-03-17 | 1985-07-16 | David Witiak | Alkali-soluble emulsion polymers in acidic surfactant compositions |
US4892916A (en) * | 1984-08-15 | 1990-01-09 | Allied Colloids Limited | Polymeric thickeners and their production |
US4978460A (en) * | 1985-05-03 | 1990-12-18 | Bluecher Hubert | Aqueous swollen macromolecule-containing system as water for firefighting |
US5190110A (en) * | 1985-05-03 | 1993-03-02 | Bluecher Hubert | Use of an aqueous swollen macromolecule-containing system as water for fire fighting |
US4745154A (en) * | 1986-04-14 | 1988-05-17 | Alco Chemical Corporation | Water soluble polymers, their preparation and their uses |
US4814514A (en) * | 1986-05-07 | 1989-03-21 | Dai-Ichi Kogyo Seiyaku Co., Ltd. | Surface active compounds having a polymerizable moiety |
US4847410A (en) * | 1987-07-30 | 1989-07-11 | Olin Corporation | Block co-polymers useful as aqueous dispersants |
US4959156A (en) * | 1987-07-30 | 1990-09-25 | Olin Corporation | Block co-polymers useful as aqueous dispersants |
US5403821A (en) * | 1988-11-09 | 1995-04-04 | Nippon Shokubai Kagaku Kogyo Co., Ltd. | Drilling fluid additives |
US5854318A (en) * | 1989-07-25 | 1998-12-29 | Nippon Shokubai Kagaku Kogyo Co, Ltd. | Cement additive, method for producing the same, and cement composition |
US5476885A (en) * | 1989-07-25 | 1995-12-19 | Nippon Shokubai Co., Ltd. | Cement additive, method for producing the same, and cement composition |
US5086142A (en) * | 1989-07-29 | 1992-02-04 | Th. Goldschmidt Ag | Copolymer acting as thickening agent for aqueous preparations having a ph above 5.5, a method for its preparation and its use as a thickening agent |
US7465774B1 (en) * | 1992-04-23 | 2008-12-16 | Basf Aktiengesellscahft | Use of copolymers of carboxylic acids and long-chain compounds with isolated C-C multiple bonds as thickeners or dispersants |
US5488180A (en) * | 1992-05-29 | 1996-01-30 | Union Carbide Chemicals & Plastics Technology Corporation | Complex hydrophobe compounds |
US5292828A (en) * | 1992-05-29 | 1994-03-08 | Union Carbide Chemicals & Plastics Technology Corporation | Polymers containing complex hydrophobic groups |
US5292843A (en) * | 1992-05-29 | 1994-03-08 | Union Carbide Chemicals & Plastics Technology Corporation | Polymers containing macromonomers |
US5401802A (en) * | 1992-05-29 | 1995-03-28 | Union Carbide Chemicals & Plastics Technology Corporation | Polymers containing complex hydrophobic groups |
US5342883A (en) * | 1992-05-29 | 1994-08-30 | Union Carbide Chemicals & Plastics Technology Corporation | Polymers containing macromonomers |
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US5486587A (en) * | 1992-05-29 | 1996-01-23 | Union Carbide Chemicals & Plastics Technology Corporation | Aqueous latexes containing macromonomers |
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Also Published As
Publication number | Publication date |
---|---|
EP0050923A2 (en) | 1982-05-05 |
CA1203347A (en) | 1986-04-15 |
EP0050923A3 (en) | 1982-10-27 |
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